CN116445158A - Glucose probe and preparation method and application thereof - Google Patents
Glucose probe and preparation method and application thereof Download PDFInfo
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- CN116445158A CN116445158A CN202310396665.8A CN202310396665A CN116445158A CN 116445158 A CN116445158 A CN 116445158A CN 202310396665 A CN202310396665 A CN 202310396665A CN 116445158 A CN116445158 A CN 116445158A
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 84
- 239000008103 glucose Substances 0.000 title claims abstract description 84
- 239000000523 sample Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001514 detection method Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 32
- 108010015776 Glucose oxidase Proteins 0.000 claims description 18
- 239000004366 Glucose oxidase Substances 0.000 claims description 18
- 229940116332 glucose oxidase Drugs 0.000 claims description 18
- 235000019420 glucose oxidase Nutrition 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 210000002966 serum Anatomy 0.000 claims description 12
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 8
- 235000018417 cysteine Nutrition 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000000171 quenching effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 238000010791 quenching Methods 0.000 abstract description 8
- 238000006862 quantum yield reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 230000005284 excitation Effects 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000007850 fluorescent dye Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229960002303 citric acid monohydrate Drugs 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229930182830 galactose Natural products 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical group O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000002096 quantum dot Substances 0.000 description 2
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- 239000012488 sample solution Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- ZULISPCCQYDDNG-UHFFFAOYSA-N zinc methanol dinitrate Chemical compound CO.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] ZULISPCCQYDDNG-UHFFFAOYSA-N 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Chemical group OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Chemical group 0.000 description 1
- 239000005715 Fructose Chemical group 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical group OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Chemical group 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical group O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Chemical group OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Chemical group OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical group OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Chemical group 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
- G01N2021/6419—Excitation at two or more wavelengths
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- General Physics & Mathematics (AREA)
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- General Health & Medical Sciences (AREA)
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
The invention relates to the field of biosensors, in particular to a glucose probe and a preparation method and application thereof. The method comprises the following steps: compounding fluorescent carbon dots with a metal organic framework material to obtain CDs-MOFs; and compositing the CDs-MOFs and nano silver to obtain the AgNPs@CDs-MOFs probe. The fluorescent carbon dots are compounded with the metal organic framework material and AgNPs in sequence, so that the fluorescent carbon dots have good dispersing effect and fluorescence quenching capability, and the probe has specific recognition performance on glucose, is used for qualitatively and quantitatively detecting glucose, and has the advantages of simplicity in operation, rapidness, high efficiency, good specificity, low minimum detection limit, wide detection range, high sensitivity, high accuracy and the like.
Description
Technical Field
The invention relates to the field of biosensors, in particular to a glucose probe and a preparation method and application thereof.
Background
The method for detecting glucose in serum mainly comprises an electrochemical method, a colorimetric method, a surface plasmon resonance method and a surface enhanced Raman scattering method, and has the problems of high equipment requirement, complex sample treatment, complex detection process and the like although the methods have excellent glucose detection performance. The fluorescent sensor has the advantages of simple operation, high sensitivity, quick response and the like, and is receiving more and more attention. Several fluorescent probes have been developed to date to detect glucose molecules, including organic dye molecules, metal nanoparticles and semiconductor quantum dots, but still suffer from significant drawbacks such as high environmental toxicity, low selectivity, poor water solubility, poor stability, etc.
The fluorescent carbon dots have the advantages of stable luminescence, good water solubility, low toxicity and the like, however, the fluorescent carbon dots have low luminescence efficiency, lower quantum yield, far less than the traditional organic dye and semiconductor quantum dots, and the self-quenching phenomenon is easy to generate when the concentration is increased, so that the accuracy and the sensitivity of the single fluorescent carbon dots as fluorescent probes are low, the wide application of the single fluorescent carbon dots is limited, and the fluorescent carbon dots are insensitive/unresponsive to glucose molecules and decomposition products thereof and cannot be directly used for detecting the glucose molecules.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the existing single fluorescent carbon point is low in accuracy and sensitivity and cannot be directly used for detecting glucose molecules, so that the glucose probe for solving the technical problem, the preparation method and the application thereof are provided, and the glucose probe has the characteristic recognition performance on glucose and has the advantages of high accuracy and high sensitivity.
The technical scheme of the invention is as follows:
a method for preparing a glucose probe, comprising the steps of: compounding fluorescent carbon dots with a metal organic framework material to obtain CDs-MOFs; and compositing the CDs-MOFs and nano silver to obtain the AgNPs@CDs-MOFs probe.
The metal organic framework material is ZIF-8.
The step of compounding the fluorescent carbon dots with the metal organic framework material comprises: mixing and stirring fluorescent carbon dots, an organic ligand, metal salt and a solvent at normal temperature to obtain CDs-MOFs;
preferably, the step of compounding the fluorescent carbon dots with the metal organic framework material is: adding a fluorescent carbon dot solution into an organic ligand solution to obtain a mixed solution, dripping a metal salt solution into the mixed solution, and stirring at normal temperature to obtain CDs-MOFs; the fluorescent carbon dot solution, the organic ligand solution and the metal salt solution all contain the solvent.
The stirring time is 1-6 h.
The volume of the fluorescent carbon dot solution is 0.5-5 mL, and the concentration is 1-10 mg/mL.
The organic ligand is 2-methylimidazole; the metal salt is zinc nitrate; the molar ratio of the organic ligand to the metal salt is (2-20): 1.
The solvent is any one of methanol, ethanol, methylene dichloride, formamide, N-dimethylformamide and water.
The step of synthesizing the CDs-MOFs further comprises the steps of washing and drying the solid formed after stirring to obtain the CDs-MOFs solid.
The fluorescent carbon dots are blue fluorescent carbon dots.
The preparation method of the blue fluorescent carbon dots comprises the following steps: mixing citric acid and cysteine, and then placing the mixture in a microwave oven for heating reaction; dissolving the solid after the microwave reaction in an organic solvent, and centrifugally separating and precipitating to obtain a supernatant which is a blue fluorescent carbon dot solution;
preferably, the molar ratio of the citric acid to the cysteine is (10-1): 1-10.
Preferably, the microwave power is 100 to 800W.
Preferably, the microwave reaction time is 1 to 10 minutes.
Preferably, the method further comprises the step of purifying the solid after the microwave reaction.
The step of compounding the CDs-MOFs with nano-silver comprises: and mixing the CDs-MOFs solution with the nano silver solution to obtain the AgNPs@CDs-MOFs probe.
The CDs-MOFs solution is an aqueous solution of CDs-MOFs, and the concentration is 0.5-2 mg/mL;
the nano silver solution is an aqueous solution of nano silver, and the concentration is 0.1-1 mM;
the mass ratio of the CDs-MOFs to the nano silver is (100-10): 1.
The glucose probe is prepared by the method.
The glucose probe is AgNPs@CDs-MOFs.
The application of the glucose probe in detecting glucose or hydrogen peroxide; preferably, in the detection of glucose concentration in serum.
A method of detecting glucose comprising the steps of: mixing a sample to be detected with a glucose oxidase solution and a solution of the glucose probe to obtain a mixed solution, detecting the fluorescence intensity of the mixed solution after reaction, and qualitatively or quantitatively detecting glucose in the sample to be detected.
And in the quantitative detection, detecting the fluorescence intensity of the mixed solution before and after the reaction to obtain the carbon point fluorescence recovery degree, and taking the carbon point fluorescence recovery degree into a standard curve to obtain the concentration of glucose in the sample to be detected, wherein the standard curve represents the relationship between the standard glucose with different concentrations and the carbon point fluorescence recovery degree.
The sample is a human serum sample.
The concentration range of the glucose oxidase solution is 10-200 mg/mL;
the concentration range of the probe is 0.5-10 mu m, calculated by the content of nano silver;
the reaction temperature is 25-40 ℃ and the reaction time is 100-150 min;
the volume ratio of the sample to be tested, the glucose oxidase solution and the probe solution is 10:10:980;
the degree of fluorescence recovery of the carbon dots is represented by the difference between the ratio of fluorescence intensity of the mixed solution after reaction and before reaction and 1.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of a glucose probe, which comprises the following steps: compounding fluorescent carbon dots with a metal organic framework material to obtain CDs-MOFs; and compositing the CDs-MOFs and nano silver to obtain the AgNPs@CDs-MOFs probe. Carbon Dots (CDs) are negatively charged and small in size (nano-scale), metal Organic Frameworks (MOFs) are positively charged and porous, have large specific surface area, and can realize effective recombination through electrostatic interaction and physical adsorption. After addition of nanosilver (AgNPs), the same is made by electrostatic actionEffective recombination of CDs-MOFs and AgNPs can be achieved by using physical adsorption. Quenching of CDs fluorescence is achieved based on Surface Plasmon Enhanced Energy Transfer (SPEET) between CDs and AgNPs, and glucose is catalytically decomposed into gluconic acid and H by glucose oxidase (GOx) 2 O 2 Due to H 2 O 2 Etching AgNPs, i.e. H 2 O 2 The AgNPs react with AgNPs, agNPs are consumed, and finally CDs fluorescence is recovered, so that the AgNPs@CDs-MOFs probe has response to glucose decomposition products, has specific recognition performance to glucose, and can realize quantitative and qualitative detection of glucose by detecting the degree of carbon point fluorescence recovery before and after reaction.
The MOFs material has the advantages that the carbon dots can be effectively dispersed due to the large specific surface area and the porous structure, fluorescence quenching caused by concentration is reduced, the quantum yield of the carbon dots is improved, meanwhile, the AgNPs effective load is also improved due to the large specific surface area and the porous structure of the MOFs material, the fluorescence quenching effect is improved, and a foundation is laid for realizing high-sensitivity detection of glucose. Therefore, in the AgNPs@CDs-MOFs probe, the carbon dots have good dispersing effect and fluorescence quenching capability, and the probe has specific recognition performance on glucose, is used for quantitatively and qualitatively detecting glucose, and has the advantages of simplicity in operation, rapidness, high efficiency, good specificity, low minimum detection limit, wide detection range, high sensitivity, high accuracy and the like. The carbon dot based probe has the advantages of stable luminescence, good water solubility, low toxicity and the like.
2. The method further selects ZIF-8 in the MOFs material for dispersing carbon dots, preferably selects fluorescent carbon dot solution, zinc nitrate and 2-methylimidazole as raw materials, methanol as a solvent, and prepares the carbon dot doped MOFs material (CDs-ZIF-8) by a one-pot method, wherein the ZIF-8 is beneficial to reducing carbon dot fluorescence quenching caused by concentration, improving the quantum yield of the carbon dots, and simultaneously beneficial to AgNPs effective load and improving fluorescence quenching effect.
3. The fluorescent carbon dot synthesis method designed by the invention has high efficiency in separation and purification and high quantum yield, and is beneficial to further improving the sensitivity and accuracy of the carbon dot-based probe. The method has low equipment requirements, can finish the preparation by a household microwave oven, and is beneficial to macro preparation, so that the method can realize the efficient and macro preparation of blue fluorescent carbon dots, and solves the problems of long time consumption and low quantum yield of the existing preparation method.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of the excitation spectrum of the blue fluorescent carbon dots of example 1 and the emission spectrum at different excitation wavelengths;
FIG. 2 is a graph of fluorescence stability of aqueous CDs-ZIF-8 solutions of example 1 under 360nm excitation;
FIG. 3 is an XRD pattern for CDs-ZIF-8 of example 1;
FIG. 4 is a graph showing the calculation result of fluorescence quantum yield of CDs solution of example 1;
FIG. 5 is a graph showing the results of calculation of fluorescence quantum yield of the aqueous CDs-ZIF-8 solution of example 1;
FIG. 6 is a ZIF-8 enhanced quenching effect;
FIG. 7 is a TEM image of AgNPs@CDs-ZIF-8 probe of example 1;
FIG. 8 shows different concentrations of H 2 O 2 Effect on the fluorescence intensity of agnps@cds-ZIF-8 of example 1;
FIG. 9 is AgNPs@CDs-ZIF-8 vs. H of example 1 2 O 2 Detecting a linear relation diagram;
FIG. 10 is a graph showing the effect of varying concentrations of glucose on the fluorescence intensity of AgNPs@CDs-ZIF-8 of example 1;
FIG. 11 is a graph of AgNPs@CDs-ZIF-8 versus glucose detection for example 1;
FIG. 12 is a graph of potential interference analysis of glucose detection by different sugars;
FIG. 13 shows different concentrations of H 2 O 2 Effect graph of the fluorescence intensity of AgNPs@CDs for comparative example 1;
FIG. 14 shows different concentrations of H 2 O 2 Effect of CDs fluorescence intensity on comparative example 2;
FIG. 15 shows different concentrations of H 2 O 2 Effect of fluorescence intensity of CDs-ZIF-8 of comparative example 3.
Detailed Description
The types of fluorescence detection instruments used for detecting the fluorescence intensity of the sample solutions in the examples and experimental examples are as follows: hitachi F4600 fluorescence spectrometer (excitation slit 10nm, emission 5 nm); the type of the instrument used for detecting the quantum yield of the sample solution is: edinburgh FLS-1000 steady state transient fluorescence spectrometer (450W xenon lamp).
Example 1
The preparation method of the AgNPs@CDs-ZIF-8 probe comprises the following steps:
(1) Fully grinding and uniformly mixing citric acid monohydrate (2 g) and cysteine (1 g) according to a molar ratio of 1.15:1, and transferring the mixture into a beaker to obtain a reaction precursor;
(2) Placing the precursor obtained in the step (1) in a household microwave oven, reacting for 1.5min under 800W power, and purifying the solid after microwave reaction by carbon dots to obtain a purified solid;
(3) Dissolving 100mg of the purified solid obtained in the step (2) in 20mL of methanol, performing ultrasonic dissolution, centrifuging at 8000rpm to remove precipitate, and obtaining supernatant to obtain 20mL of blue fluorescent carbon dot solution with the concentration of 5mg/mL and the Quantum Yield (QY) of 50.88%;
(4) Adding 1mL (5 mg/mL) of the supernatant obtained in the step (3) into a methanol solution (19.76 mM,50 mL) dissolved with 2-methylimidazole to obtain a mixed solution, magnetically stirring for 30min, dropwise adding a zinc nitrate methanol solution (0.123M, 1 mL) into the mixed solution, magnetically stirring for 1h when a milky solid is generated, and stopping stirring;
(5) Centrifuging the solid obtained in the step (4), washing with methanol, and drying to obtain CDs-ZIF-8 solid;
(6) Dissolving the CDs-ZIF-8 solid obtained in the step (5) in water to prepare 0.8mg/mL aqueous solution (the quantum yield is 56.81%), taking 0.4mL AgNPs solution (0.25 mM) and 0.6mL of the CDs-ZIF-8 solution, fully mixing (the mass ratio of the CDs-MOFs solid to the nano silver is 44.5:1), and magnetically stirring for 30min to obtain 10 mu M AgNPs@CDs-ZIF-8 solution calculated according to the nano silver content.
FIG. 1 is a graph of the excitation spectrum and the emission spectrum of the blue fluorescent carbon dot solution prepared in the step (3) of example 1 at different excitation wavelengths. The spectrum shows that the optimal excitation wavelength of the blue fluorescent carbon dot aqueous solution is 360nm, and the optimal emission peak is 440 nm. Along with the change of the excitation wavelength, the emission peak position of the blue fluorescent carbon point is kept unchanged, and only the fluorescence intensity is changed, which indicates that the blue fluorescent carbon point prepared by the invention has the independence of the excitation wavelength.
FIG. 2 is a graph showing fluorescence stability of the CDs-ZIF-8 aqueous solution prepared in step (6) of example 1 under continuous excitation at 360 nm. The spectrogram shows that the material has stable fluorescence performance, and the fluorescence intensity is basically not attenuated after being continuously excited for 1 h.
FIG. 3 is an XRD pattern of CDs-ZIF-8 solid prepared in step (5) of example 1. The peak position is consistent with the ZIF-8 standard spectrogram, which shows that the CDs doped ZIF-8 material is successfully prepared.
Fig. 4 is a graph showing the calculated fluorescence quantum yield of the blue fluorescent carbon dot solution prepared in the step (3) of example 1, and fig. 5 is a graph showing the calculated fluorescence quantum yield of the CDs-ZIF-8 aqueous solution prepared in the step (6) of example 1, and the result shows that ZIF-8 has the effect of dispersing carbon dots, can reduce fluorescence quenching caused by concentration of carbon dots, and has the capability of improving the fluorescence quantum yield of carbon dots at a certain concentration.
FIG. 6 shows that, in the AgNPs@CDs-ZIF-8 (CDs+ZIF-8+AgNPs in the figure) probe obtained in example 1, ZIF-8 has an effect of significantly enhancing quenching of CDs by AgNPs, relative to the AgNPs@CDs (CDs+AgNPs in the figure) probe of comparative example 1. This is mainly due to the fact that AgNPs can be fully compounded with CDs on the surface of ZIF-8 through electrostatic interaction and physical adsorption, so that the energy resonance transfer capacity is enhanced, and a good quenching effect is achieved. Lays a foundation for the subsequent improvement of the glucose detection sensitivity and the expansion of the detection range.
FIG. 7 is a TEM image of AgNPs@CDs-ZIF-8 probe prepared in step (6) of example 1. The images show that the probe size is about 300nm, and carbon dots and nano silver are uniformly distributed around.
Example 2
The preparation method of the AgNPs@CDs-ZIF-8 probe in the embodiment is different from that in the embodiment 1 in that the addition amount of the AgNPs solution in the step (6) is 0.8mL, and the mass ratio of CDs-MOFs solid to nano-silver is 44.5:2.
Example 3
The preparation method of the AgNPs@CDs-ZIF-8 probe in the embodiment is different from that in the embodiment 1 in that the addition amount of the AgNPs solution in the step (6) is 1.2mL, and the mass ratio of CDs-MOFs solid to nano-silver is 14.8:1.
Example 4
The preparation method of the AgNPs@CDs-ZIF-8 probe in the embodiment is different from that in the embodiment 1 in that the addition amount of the AgNPs solution in the step (6) is 0.2mL, and the mass ratio of CDs-MOFs solid to nano silver is 89:1.
Example 5
This example provides a method for detecting glucose using the AgNPs@CDs-ZIF-8 probe of example 1, comprising the steps of:
experimental group: mixing 10 mu L of a sample to be detected with 10 mu L of glucose oxidase solution (10 mg/mL) and 980 mu L of AgNPs@CDs-ZIF-8 solution (10 mu M) to obtain a mixed solution, reacting at 37 ℃ for 100min, detecting the fluorescence intensity of the mixed solution, and qualitatively or quantitatively detecting glucose in the sample to be detected.
Blank group: 10 mu L of a sample to be detected is mixed with 10 mu L of glucose oxidase solution (10 mg/mL) and 980 mu L of deionized water to obtain a mixed solution, and the mixed solution is reacted for 100min at 37 ℃ to detect the fluorescence intensity.
In the qualitative detection, compared with a blank group, the fluorescence of the experimental group is enhanced (the fluorescence is enhanced by the instrument detection or 365nm handheld ultraviolet lamp irradiation), which indicates that the sample contains glucose.
In the quantitative detection, standard glucose solutions with different concentrations are used as standard substances, and the fluorescence intensity of the mixed solution before and after the reaction is detected by the concentration of glucose and F/F 0 -1 relationship to draw a standard curve, F 0 F is the fluorescence intensity of the mixed solution before reaction, F is the fluorescence intensity of the mixed solution after reaction, F/F of the sample to be detected 0 -1 substituting the standard curveAnd in the line, calculating to obtain the concentration of glucose in the sample to be detected. The standard curve in this example was the standard curve in experimental example 2, see fig. 11.
Comparative example 1
The preparation method of the AgNPs@CDs probe comprises the following steps:
(1) Fully grinding and uniformly mixing citric acid monohydrate (2 g) and cysteine (1 g) according to a molar ratio of 1.15:1, and transferring the mixture into a beaker to obtain a reaction precursor;
(2) Placing the precursor obtained in the step (1) in a household microwave oven, reacting for 1.5min under 800W power, and purifying the solid after microwave reaction by carbon dots to obtain a purified solid;
(3) Dissolving 100mg of the purified solid obtained in the step (2) in 20mL of methanol, performing ultrasonic dissolution, centrifuging at 8000rpm to remove precipitate, and obtaining supernatant to obtain 20mL of blue fluorescent carbon dot solution with the concentration of 5mg/mL and the quantum yield of 50.88%;
(4) Adding 0.1mL of the supernatant obtained in the step (3) into 0.4mL of AgNPs solution (0.25 mM), diluting the solution to 1mL by deionized water, magnetically stirring the solution for 30min, centrifuging the solution at 8000rpm, washing the solution to obtain AgNPs@CDs, and dissolving the AgNPs@CDs to 8mL by deionized water to obtain 10 mu M of AgNPs@CDs solution, wherein the content of nano silver is calculated.
Comparative example 2
The preparation method of the carbon dot fluorescent probe comprises the following steps:
(1) Fully grinding and uniformly mixing citric acid monohydrate (2 g) and cysteine (1 g) according to a molar ratio of 1.15:1, and transferring the mixture into a beaker to obtain a reaction precursor;
(2) Placing the precursor obtained in the step (1) in a household microwave oven, reacting for 1.5min under 800W power, and purifying the solid after microwave reaction by carbon dots to obtain a purified solid;
(3) Dissolving 100mg of the purified solid obtained in the step (2) in 20mL of methanol, performing ultrasonic dissolution, centrifuging at 8000rpm to remove precipitate, and obtaining supernatant to obtain 20mL of blue fluorescent carbon dot solution with the concentration of 5mg/mL and the quantum yield of 50.88%;
(4) The supernatant was freeze-dried to obtain carbon dot solid powder, and deionized water was used to prepare an aqueous carbon dot solution having a carbon dot concentration of 10. Mu.g/mL.
Comparative example 3
A preparation method of a CDs-ZIF-8 fluorescent probe comprises the following steps:
(1) Fully grinding and uniformly mixing citric acid monohydrate (2 g) and cysteine (1 g) according to a molar ratio of 1.15:1, and transferring the mixture into a beaker to obtain a reaction precursor;
(2) Placing the precursor obtained in the step (1) in a household microwave oven, reacting for 1.5min under 800W power, and purifying the solid after microwave reaction by carbon dots to obtain a purified solid;
(3) Dissolving 100mg of the purified solid obtained in the step (2) in 20mL of methanol, performing ultrasonic dissolution, centrifuging at 8000rpm to remove precipitate, and obtaining supernatant to obtain 20mL of blue fluorescent carbon dot solution with the concentration of 5mg/mL and the quantum yield of 50.88%;
(4) Adding 1mL (5 mg/mL) of the supernatant obtained in the step (3) into a methanol solution (19.76 mM,50 mL) dissolved with 2-methylimidazole to obtain a mixed solution, magnetically stirring for 30min, dropwise adding a zinc nitrate methanol solution (0.123M, 1 mL) into the mixed solution, magnetically stirring for 1h when a milky solid is generated, and stopping stirring;
(5) Centrifuging the solid obtained in the step (4), washing with methanol, and drying to obtain CDs-ZIF-8 solid;
(6) The CDs-ZIF-8 solid is dissolved by deionized water to prepare a CDs-ZIF-8 solution with the concentration of 0.8 mg/mL.
Experimental example 1
20 mu L of H with different concentrations 2 O 2 Solution (H) 2 O 2 Final concentrations of 0. Mu.M, 5. Mu.M, 10. Mu.M, 20. Mu.M, 40. Mu.M, 60. Mu.M, 80. Mu.M, 100. Mu.M, 120. Mu.M, 150. Mu.M, 200. Mu.M, 300. Mu.M, 500. Mu.M, 1000. Mu.M) were added to 980. Mu.L of the AgNPs@CDs-ZIF-8 solution (10. Mu.M) obtained in example 1 to obtain a mixed solution, and after a reaction at 37℃for 100 minutes, the fluorescence intensities of the mixed solution before and after the reaction were measured to obtain the degree of recovery of carbon point fluorescence (F/F) 0 -1), the results are shown in fig. 8 and 9.
The AgNPs@CDs-ZIF-8 solution obtained in example 1 was replaced with the same volume of the AgNPs@CDs solution of comparative example 1, the carbon dot aqueous solution of comparative example 2 and the CDs-ZIF-8 solution of comparative example 3 in the same manner as described above, and the results are shown in FIGS. 13 to 14, respectively.
The results of FIGS. 8 and 9 show that, with H 2 O 2 The fluorescence intensity of AgNPs@CDs-ZIF-8 is gradually enhanced by increasing the concentration, the amplitude change is obvious, and H 2 O 2 At a concentration of 100. Mu.M, F/F 0 2.8. Has good linear relation when the concentration is 5-100 mu M, the fitting linear equation is y=0.18717+0.0155x, and the fitting coefficient R 2 =0.995. Wherein x is H 2 O 2 Is the concentration of Y is F/F 0 -1，F 0 Is not added with H 2 O 2 The fluorescence intensity of the mixed solution before the reaction is that F is added with H 2 O 2 And the fluorescence intensity of the mixed solution after the reaction. The minimum limit of detection is 3.3. Mu.M.
FIG. 13 shows that with H 2 O 2 The increase of the concentration gradually increases the fluorescence intensity of AgNPs@CDs, but the increase amplitude is slower, H 2 O 2 At a concentration of 100. Mu.M, F/F 0 1.2, the detection sensitivity is low.
FIG. 14 shows different concentrations of H 2 O 2 Has no influence on the fluorescence intensity of the carbon point, namely the decomposition product H of the carbon point on glucose 2 O 2 Almost no response. Therefore, carbon-point fluorescent probes are not suitable for detecting glucose in combination with glucose oxidase.
FIG. 15 shows that different concentrations H 2 O 2 Has no influence on the fluorescence intensity of the CDs-ZIF-8, namely the decomposition product H of the CDs-ZIF-8 on glucose 2 O 2 Almost no response. Thus, CDs-ZIF-8 fluorescent probes are also unsuitable for detecting glucose in conjunction with glucose oxidase.
Therefore, none of the four materials, CDs-ZIF-8, agNPs@CDs-ZIF-8, are suitable for detecting glucose in combination with glucose oxidase, and AgNPs@CDs-ZIF-8 vs. H 2 O 2 The highest detection sensitivity is suitable for detecting glucose in combination with glucose oxidase.
Experimental example 2
mu.L of aqueous glucose oxidase solution (10 mg/mL) and 10. Mu.L of the differentGlucose solutions (final concentrations of 0. Mu.M, 5. Mu.M, 10. Mu.M, 20. Mu.M, 40. Mu.M, 60. Mu.M, 80. Mu.M, 100. Mu.M, 120. Mu.M, 150. Mu.M, 200. Mu.M, 300. Mu.M, 500. Mu.M, 1000. Mu.M) were added to 980. Mu.L of AgNPs@CDs-ZIF-8 solution (10. Mu.M) obtained in example 1 to obtain a mixture, and after a reaction at 37℃for 100 minutes, the fluorescence intensities of the mixture before and after the reaction were measured to obtain the degree of recovery of carbon point fluorescence (F/F) 0 -1), the results are shown in fig. 10, fig. 11 and table 1.
Glucose oxidase catalyzes the decomposition of glucose to produce H 2 O 2 ，H 2 O 2 The fluorescence of the etched AgNPs and CDs is recovered, and the linear relationship between the fluorescence intensity change and the glucose detection is shown in FIG. 10 and FIG. 11. The results show that the fluorescence intensity of AgNPs@CDs-ZIF-8 is gradually enhanced with the increase of the glucose concentration, and the amplitude is obvious. Has good linear relation when the concentration is 5-150 mu M, the fitting linear equation is y=0.01868+0.00567 x, and the fitting coefficient R 2 =0.995. Wherein x is the concentration of glucose and y is F/F 0 -1，F 0 The pre-reaction fluorescence intensity is the fluorescence intensity before glucose is added, and the fluorescence intensity after glucose is added and reacted. The minimum detection limit is 3.1 mu M, the detection range is 5-150 mu M, and the sensitivity is high.
Glucose standard curve test was performed according to the above method using AgNPs@CDs-ZIF-8 solution obtained in examples 2-4, and the test results are shown in Table 1.
TABLE 1 glucose calibration curve test results for examples 1-4
| Minimum detection limit (mu M) | Detection range | |
| Example 1 | 3.1 | 5-150μM |
| Example 2 | 5.9 | 5-120μM |
| Example 3 | 6.1 | 20-200μM |
| Example 4 | 5.7 | 10-120μM |
The results in Table 1 show that the AgNPs@CDs-ZIF-8 probes obtained in examples 1-4 of the application can be used for detecting glucose, and have the advantages of low minimum detection limit, wide detection range and high sensitivity.
Experimental example 3
The specificity of the AgNPs@CDs-ZIF-8 probe obtained in example 1 for glucose detection was verified. 10. Mu.L of galactose (40 mM), 10. Mu.L of glucose oxidase aqueous solution (10 mg/mL) were added to 980. Mu.L of AgNPs@CDs-ZIF-8 solution (10. Mu.M) obtained in example 1 to obtain a mixed solution, and after reaction at 37℃for 100 minutes, the fluorescence intensity of the mixed solution before and after the reaction was measured to obtain the degree of recovery of carbon point fluorescence (F/F) 0 -1), the result is shown in FIG. 12. The results of the test with galactose replaced with mannose, fructose, xylose, sucrose, and maltose in equal concentrations and volumes are shown in fig. 12. The results of the test with galactose replaced with an equal volume of glucose (concentration 4 mM) are shown in FIG. 12.
FIG. 12 shows that the interference to glucose detection is still small when the various interfering sugar concentrations are 10 times the glucose concentration, indicating that the probe has good specificity for glucose detection.
Experimental example 4
Using example 1The prepared AgNPs@CDs-ZIF-8 probe is used for detecting glucose in human serum, and the results are shown in Table 2. The experimental process comprises the following steps: a group of samples were obtained by taking 10. Mu.L of human serum sample and 10. Mu.L of glucose oxidase aqueous solution (10 mg/mL) and adding to 980. Mu.L of LAgNPs@CDs-ZIF-8 solution (10. Mu.M) obtained in example 1 to obtain a mixed solution, reacting at 37℃for 100min, and detecting the fluorescence intensity of the mixed solution before and after the reaction to obtain the degree of recovery of carbon point fluorescence (F/F) 0 -1) substituting into the standard curve in experimental example 2 to obtain the initial concentration of glucose in serum; another group of the same samples were obtained by taking human serum samples 10. Mu.L and 10. Mu.L of an aqueous glucose oxidase solution (10 mg/mL) and adding to 980. Mu.L of the AgNPs@CDs-ZIF-8 solution (10. Mu.M) obtained in example 1 to obtain a mixed solution, adding 2. Mu.L of a 20mM aqueous glucose solution (adding final concentration of 40. Mu.M), reacting at 37℃for 100 minutes, and detecting the fluorescence recovery degree of the mixed solution to obtain the total concentration of glucose. The ratio of the difference between the two measured glucose concentrations to the added glucose concentration (40 uM) gave the addition-standard recovery, and the detection results are shown in Table 2.
The AgNPs@CDs-ZIF-8 probe obtained in examples 2-4 was used to test the concentration of glucose in serum sample 1 as well as the concentration of glucose after labeling, as described above, and the results are shown in Table 2.
TABLE 2 results of glucose concentration in human serum samples
The results in Table 2 show that the AgNPs@CDs-ZIF-8 probes obtained in examples 1-4 of the application can be used for detecting glucose in human serum samples, and the detection results have good stability and accuracy.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A method for preparing a glucose probe, comprising the steps of: compounding fluorescent carbon dots with a metal organic framework material to obtain CDs-MOFs; and compositing the CDs-MOFs and nano silver to obtain the AgNPs@CDs-MOFs probe.
2. The method of claim 1, wherein the metal organic framework material is ZIF-8.
3. The method of claim 2, wherein the step of compounding the fluorescent carbon dots with the metal-organic framework material comprises: mixing and stirring fluorescent carbon dots, an organic ligand, metal salt and a solvent at normal temperature to obtain CDs-MOFs;
preferably, the step of compounding the fluorescent carbon dots with the metal organic framework material is: adding a fluorescent carbon dot solution into an organic ligand solution to obtain a mixed solution, dripping a metal salt solution into the mixed solution, and stirring at normal temperature to obtain CDs-MOFs; the fluorescent carbon dot solution, the organic ligand solution and the metal salt solution all contain the solvent.
4. A method according to claim 3, wherein the stirring time is 1 to 6 hours;
and/or the volume of the fluorescent carbon dot solution is 0.5-5 mL, and the concentration is 1-10 mg/mL;
and/or the organic ligand is 2-methylimidazole; the metal salt is zinc nitrate; the molar ratio of the organic ligand to the metal salt is (2-20): 1;
and/or the solvent is any one of methanol, ethanol, dichloromethane, formamide, N-dimethylformamide and water;
and/or the step of synthesizing the CDs-MOFs further comprises the steps of washing and drying the solid formed after stirring to obtain the CDs-MOFs solid.
5. The method of any one of claims 1-4, wherein the fluorescent carbon dots are blue fluorescent carbon dots;
the preparation method of the blue fluorescent carbon dots comprises the following steps: mixing citric acid and cysteine, and then placing the mixture in a microwave oven for heating reaction; dissolving the solid after the microwave reaction in an organic solvent, and centrifugally separating and precipitating to obtain a supernatant which is a blue fluorescent carbon dot solution;
preferably, the mole ratio of the citric acid to the cysteine is (10-1): 1-10;
preferably, the microwave power is 100-800W;
preferably, the microwave reaction time is 1-10 min;
preferably, the method further comprises the step of purifying the solid after the microwave reaction.
6. The method of any one of claims 1-5, wherein the step of complexing the CDs-MOFs with nano-silver comprises: and mixing the CDs-MOFs solution with the nano silver solution to obtain the AgNPs@CDs-MOFs probe.
7. The method of claim 6, wherein the CDs-MOFs solution is an aqueous solution of CDs-MOFs at a concentration of 0.5-2 mg/mL;
and/or the nano silver solution is an aqueous solution of nano silver, and the concentration is 0.1-1 mM;
and/or the mass ratio of CDs-MOFs to silver nanometer is (100-10): 1.
8. a glucose probe prepared by the method of any one of claims 1-7.
9. Use of the glucose probe of claim 8 for detecting glucose or hydrogen peroxide;
preferably, in the detection of glucose concentration in serum.
10. A method for detecting glucose, comprising the steps of: mixing a sample to be detected with a glucose oxidase solution and the solution of the glucose probe according to claim 8 to obtain a mixed solution, detecting the fluorescence intensity of the mixed solution after reaction, and qualitatively or quantitatively detecting glucose in the sample to be detected;
preferably, during quantitative detection, detecting the fluorescence intensity of the mixed solution before and after the reaction to obtain the carbon point fluorescence recovery degree, and bringing the carbon point fluorescence recovery degree into a standard curve to obtain the concentration of glucose in a sample to be detected, wherein the standard curve represents the relationship between the standard glucose with different concentrations and the carbon point fluorescence recovery degree;
preferably, the sample is a human serum sample;
preferably, the concentration range of the glucose oxidase solution is 10-200 mg/mL;
preferably, the concentration range of the probe is 0.5-10 mu m, calculated by the content of nano silver;
preferably, the reaction temperature is 25-40 ℃ and the reaction time is 100-150 min;
preferably, the degree of carbon point fluorescence recovery is represented by a difference between the ratio of fluorescence intensity of the mixture after the reaction and before the reaction and 1.
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